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Aqueous Corrosion of Nuclear Glasses : Influence of Disposal Conditions

Obiettivo

Three major avenues of research will be investigated in a programme combining an experimental approach and modelling of relational processes to characterize and quantify the potential reaction mechanisms of glass matrix corrosion and the degree of radionuclide containment : < basic research on aqueous corrosion of nuclear glass; > the effect of the host rock on R7T7 glass alteration; and finally the development of models describing glass behaviour in repository conditions.
Geological disposal of vitrified high level waste packages will expose the containment glass to multiple complex chemical reactions (involving the host rock, the engineered barrier materials and the nuclear glass) due to the presence of the water vector in the repository environment. The presence of environmental or local site materials affects (increases or decreases) the glass matrix corrosion rates and the degree of radionuclide containment. It is therefore essential to characterize and quantify the potential reaction mechanisms in a geological disposal complex. The investigation begins at laboratory scale; the experimental approach also allows the development of a nuclear glass dissolution model applicable to actual repository conditions.

3 major avenues of research will be investigated in a programme combining an experimental approach and modelling of relational processes: basic research on aqueous corrosion of nuclear glass; the effect of the host rock on R7T7 glass alteration; and the development of models describing glass behaviour in repository conditions.

The initial dissolution rates, equilibrium limits and equilibrium pH values were determined by 3 ICP analysis of the alteration solutions for magnesium enriched R7T7 glass and for M7 glass, which contains less silica then R7T7 glass. Crystallographic and chemical investigations of the alteration products that form on the surface of these 2 type of glass are now in progress. The experimental protocol is now being specified to investigate the effects of the ionic strength on the initial R7T7 glass corrosion kinetic. The experiments required to determine the R7T7 glass equilibrium limits in the presence of 5 site materials have all been initiated.
Work programme:

Basic research on aqueous corrosion of nuclear glass
The effect of glass composition on the initial dissolution rate, the solubility limit and equilibrium pH, and the role of new phases on glass dissolution kinetics will be investigated by varying the concentrations of the following components: MgO, SiO2, Al2O3, B2O3 and fission product oxides.
Role of exterior ions: metallic cations (Al, Fe, Zn, Pb and Mg) and canister corrosion products; effect of the ionic strength.
Investigation of the interface gel layer: physical and chemical properties, thermodynamic properties and stability.

Influence of the disposal site
Equilibrium limits with various host materials : granite, clay (ref 448 and 802), schist and salt.
Parameter experiments at 90 C in the presence of schist (different types and grain sizes), clay, granite or salt (clear halite and cloudy halite).
Integral experiments with granite, clay and schist.

Development of a glass behaviour model
Mechanistic model
Geochemical model (thermodynamics and kinetics of R7T7 glass dissolution, interactions between R7T7 glass and corrosion products, interactions between R7T7 glass and host materials : granite, clay or schist).

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Coordinatore

Commissariat à l'Energie Atomique (CEA)
Contributo UE
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Indirizzo
Centre d'Études Nucléaires de la Vallée du Rhône Cité de Marcoule
30205 Bagnols-sur-Cèze
Francia

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